DE3121156A1 - XYLITE DERIVATIVES, METHOD FOR THE PRODUCTION OF THESE COMPOUNDS AND THEIR CONTAINING AGENTS WITH GROWTH REGULATORY EFFECT FOR PLANTS - Google Patents

Abstract

1 The invention relates to new xylitol derivatives of the general formula I in which R [deep] 1, R [deep] 2, R [deep] 3 and R [deep] 4 are identical or different and each is hydrogen, a C [deep] 1-C [deep] 10-alkyl radical, a C [deep] 1-C [deep] 10-alkyl radical which is mono- or polysubstituted by halogen, C [deep] 1-C [deep] 6-alkoxy, phenoxy and / or halophenoxy Aryl-C [deep] 1-C [deep] 3-alkyl radical, one or more than one through C [deep] 1-C [deep] 6-alkyl, halogen, C [deep] 1-C [deep] 6- Alkoxy, nitro and / or trifluoromethyl substituted aryl-C [deep] 1-C [deep] 3-alkyl radical, a C [deep] 3-C [deep] 8-cycloaliphatic hydrocarbon radical, an aromatic hydrocarbon radical or one or more times C [deep] 1-C [deep] 6-alkyl, halogen, C [deep] 1-C [deep] 6-alkoxy, nitro and / or trifluoromethyl substituted aromatic hydrocarbon radicals or R [deep] 1 and R [deep] 2 and / or R [deep] 3 and R [deep] 4 together with the adjacent carbon atom form a C [deep] 3-C [deep] 8-cycloaliphatic hydrocarbon est, R [deep] 5 is hydrogen or a C [deep] 1-C [deep] 4-alkyl radical and R [deep] 6 is an aromatic hydrocarbon radical or one or more times through C [deep] 1-C [deep] 6 -Alkyl, C [deep] 1-C [deep] 6-alkoxy, phenoxy, phenyl, halogen, nitro and / or trifluoromethyl-substituted aromatic hydrocarbon radicals, processes for the preparation of these compounds and agents containing them with a growth-regulating effect. The compounds are particularly suitable for influencing the vegetative and generative growth of legumes such as soy.

Description

The invention relates to new xylitol derivatives, processes for the preparation of these compounds and agents containing them and having a growth-regulating effect on plants.

Compounds with a growth-regulating effect are already known and in some cases have even been introduced into practice.

One of these practice-known products based on triiodobenzoic acid influences the growth of plants, but does not always have a satisfactory effect.

Another product based on 2,3: 4,6-di-O-isopropylidene-2-ketogulonic acid and its sodium salt, on the other hand, leads to morphological changes in some ornamental and cultivated plants, but is limited in terms of its use to certain plants.

The object of the present invention is to provide an agent which has a growth-regulating effect with a broad spectrum of activity while at the same time protecting the plants.

The object is achieved according to the invention by an agent which is characterized by a content of at least one compound of the general formula I.

where R [deep] 1, R [deep] 2, R [deep] 3 and R [deep] 4 are identical or different and each is hydrogen, a C [deep] 1-C [deep] 10-alkyl radical, a or C [deep] 1-C [deep] 10-alkyl radical substituted several times by halogen, C [deep] 1-C [deep] 6-alkoxy, phenoxy and / or halophenoxy, an aryl-C [deep] 1-C [ deep] 3-alkyl radical, an aryl substituted one or more times by C [deep] 1-C [deep] 6-alkyl, halogen, C [deep] 1-C [deep] 6-alkoxy, nitro and / or trifluoromethyl C [deep] 1-C [deep] 3-alkyl radical, a C [deep] 3-C [deep] 8-cycloaliphatic hydrocarbon radical, an aromatic hydrocarbon radical or a single or multiple through C [deep] 1-C [deep] 6-alkyl, halogen, C [deep] 1-C [deep] 6-alkoxy, nitro and / or trifluoro methyl substituted aromatic hydrocarbon radical or R [deep] 1 and R [deep] 2 and / or R [deep] 3 and R [deep] 4 together with the adjacent carbon atom a C [deep] 3-C [deep] 8- cycloaliphatic hydrocarbon radical, R [deep] 5 hydrogen or a C [deep] 1-C [deep] 4-alkyl radical and R [deep] 6 an aromatic hydrocarbon radical or one or more times through C [deep] 1-C [deep] 6-alkyl, C [deep] 1-C [deep] 6-alkoxy, phenoxy, phenyl, halogen, nitro and / or trifluoromethyl substituted aromatic hydrocarbon radicals.

The compounds according to the invention occur as optical and, if appropriate, also as geometric isomers. The individual isomers and their mixtures are also part of the subject matter of the invention.

The compounds according to the invention are outstandingly suitable for regulating plant growth in various crop plants and, in their spectrum of activity and in their tolerability, surprisingly surpass the above-mentioned, practice-known products with the same direction of action.

Since the compounds according to the invention cause both qualitative and quantitative changes in plants and changes in the metabolism of plants, they are in the

Class of plant growth regulators, which are characterized by the following possible applications.

Inhibition of vegetative growth in woody and herbaceous plants, for example on roadsides, railroad tracks, etc., in order to prevent excessive growth. Growth inhibition in the case of grain to prevent storage or twisting, in the case of cotton to increase the yield.

Influencing the branching of vegetative and generative organs in ornamental or cultivated plants to increase the flower base or in tobacco and tomato to inhibit side shoots.

Improvement of the fruit quality, for example an increase in the sugar content of sugar cane, sugar beet or fruit, and a more uniform ripening of the harvest, which leads to higher yields.

Increasing the resistance to climatic influences such as cold and drought.

Influencing the latex flow in rubber plants.

Formation of parthenocarpic fruits, male sterility and sexual influence are also possible applications.

Control of the germination of seeds or the emergence of buds.

Defoliation or influencing of fruit fall to facilitate harvest.

The compounds according to the invention are particularly suitable for influencing the vegetative and generative growth of some legumes, such as, for example, soy.

The application rates are generally from 0.005 to 5 kg of active ingredient / ha, depending on the intended use, but higher application rates can also be used if necessary.

The application time depends on the application goal and the climatic conditions.

Of the compounds according to the invention, the effects described are particularly notable for those at those in the above general formula IR [deep] 1, R [deep] 2, R [deep] 3 and R [deep] 4 are identical or different and are each hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, 2,2-dimethyl-1-propyl, n-pentyl, n-heptyl, n-octyl, n-decyl, chloromethyl, bromomethyl, fluoromethyl, dichloromethyl, trifluoromethyl, trichloromethyl, methyl, Methoxymethyl, ethoxymethyl, phenoxymethyl, 4-chlorophenoxymethyl, chloroethyl, bromoethyl, 2-ethoxyethyl, 2-phenoxyethyl, cyclopropyl, cyclopentyl, cyclohexyl, benzyl, 2-phenylethyl, phenyl, 2-chlorophenyl, 3-chlorophenyl, 3-chlorophenyl, 4-dichlorophenyl, 4-methoxyphenyl, 4-nitrophenyl, 2,4-dichlorophenyl, R [deep] 5 hydrogen or methyl and R [deep] 6 phenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2,6- Dichlorophenyl, 2,4-dichlorophenyl, 3,4-dichlorophenyl, 2,4,6-trichlorophenyl, 4-bromophenyl, 2,4-dibromophenyl, 2,6-dibromophenyl, 2,4,6-tribromophenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2,4-difluorophenyl, 2-methylphenyl , 3-methylphenyl, 4-methylphenyl, 3,4-dimethylphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 3,4-dioxymethylenephenyl, 2-phenoxyphenyl, 3-phenoxyphenyl, 2-nitrophenyl, 3-nitrophenyl or 4 Represent -nitrophenyl.

Particular mention should be made of compounds with an outstanding effect

5-O- (2,6-dichlorobenzyl) -1,2: 3,4-bis-O-isopropylidene-xylitol,

5-O- (2,6-dichlorobenzyl) -1,2: 3,4-bis-O- (ethyl-methyl-methylene) -xylitol and

5-0- (2,6-dichlorobenzyl) -1,2: 3,4-bis-O- (methyl-propyl-methylene) -xylitol

The compounds according to the invention can be used either alone, in a mixture with one another or with other active ingredients. Optionally, defoliation agents, crop protection agents or pest control agents can be added depending on the desired purpose.

If a broadening of the spectrum of activity is intended, other biocides can also be added. For example, active ingredients from the group of triazines, aminotriazoles, anilides, diazines, uracils, aliphatic carboxylic acids and halocarboxylic acids, substituted benzoic acids and aryl carboxylic acids, hydrazides, amides, nitriles, esters of such carboxylic acids, carbamic acid and thiocarbamic acid esters are suitable as herbicidally active mixing partners , 3,6-trichlorobenzyloxypropanil, rhodanic agents and other additives.

Other additives also include, for example, non-phytotoxic additives which, with herbicides, can produce a synergistic increase in effectiveness, such as, inter alia, wetting agents, emulsifiers, solvents and oily additives.

The active ingredients according to the invention or their mixtures are expediently in the form of preparations, such as powders, scattering agents, granules, solutions, emulsions or suspensions, with the addition of liquid and / or solid carriers or diluents and optionally wetting agents, adhesives, emulsifiers and / or dispersants, applied.

Suitable liquid carriers are, for example, water, aliphatic and aromatic hydrocarbons, such as benzene, toluene, xylene, cyclohexanone, isophorone, dimethyl sulfoxide, dimethylformamide, and mineral oil fractions.

Mineral earths, for example Tonsil, silica gel, talc, kaolin, attaclay, limestone, silicic acid and vegetable products, for example flour, are suitable as solid carriers.

Examples of surface-active substances are calcium ligninsulphonate, polyoxyethylene alkylphenol ethers, naphthalenesulphonic acids and their salts, phenolsulphonic acids and their salts, formaldehyde condensates, fatty alcohol sulphates and substituted benzenesulphonic acids and their salts.

The proportion of the active ingredient (s) in the various preparations can vary within wide limits. For example, the agents contain about 10 to 80 percent by weight of active ingredients, about 90 to 20 percent by weight of liquid or solid carriers and optionally up to 20 percent by weight of surface-active substances.

The agents can be applied in the usual way, for example with water as the carrier in spray mixture quantities of about 100 to 1000 liters / ha. An application of the means in the so-called low-volume and ultra-low-volume process is just as possible as their application in the form of so-called microgranules.

For example, the following ingredients are used to produce the preparations:

A. wettable powder

a) 40 percent by weight of active ingredient

25 percent by weight clay minerals

20 percent by weight Wesseling

10 weight percent cell pitch

5 percent by weight of surface-active substances based on a mixture of the calcium salt of lignin sulfonic acid with alkylphenol polyglycol ethers

b) 25 percent by weight of active ingredient

60 percent by weight kaolin

10 percent by weight Wesseling

5 percent by weight of surface-active substances based on the sodium salt of N-methyl-N-oleyl-taurine and the calcium salt of lignin sulfonic acid

c) 10 percent by weight of active ingredient

60 percent by weight clay minerals

15 percent by weight Wesseling

10 weight percent cell pitch

5 percent by weight of surface-active substances based on the sodium salt of N-methyl-N-oleyl-taurine and the calcium salt of lignin sulfonic acid

B. Paste

45 percent by weight active ingredient

5 weight percent sodium aluminum silicate

15 percent by weight of cetyl polyglycol ether with 8 moles of ethylene oxide

2 percent by weight spindle oil

10 weight percent polyethylene glycol

23 parts of water

C. Emulsion concentrate

25 percent by weight active ingredient

15 weight percent cyclohexanone

55 percent by weight xylene

5 percent by weight mixture of nonylphenyl polyoxyethylene or calcium dodecylbenzenesulfonate

The new compounds according to the invention can be prepared, for example, by

A) Compounds of the general formula II

with compounds of the general formula III

in the presence of acid binders

or

B) compounds of the general formula IV a) with compounds of the general formulas V

and VI

in the presence of acidic catalysts and dehydrating agents

or

b) with compounds of the general formulas VII

and VIII

in the presence of acidic catalysts, where R [deep] 1, R [deep] 2, R [deep] 3, R [deep] 4, R [deep] 5 and R [deep] 6 have the meaning given above have, R [deep] 7 and R [deep] 8 are identical or different and represent C [deep] 1-C [deep] 4-alkyl and X and Y are different and each represent a halogen atom or the group OZ in which Z represents a hydrogen atom or an equivalent of an alkali or alkaline earth metal, preferably a sodium, potassium or lithium atom.

If Z represents a hydrogen atom, the reaction is carried out in the presence of a base, expediently an alkali metal hydroxide, alkali metal alcoholate, alkali metal hydride or alkali metal carbonate, preferably a sodium compound.

A preferred embodiment of process alternative A is the reaction of a compound of the general formula II, in which Y is a hydroxyl group, with compounds of the general formula III, in which X is a halogen atom, preferably a chlorine or bromine atom, in the presence of a base, for example sodium hydride or sodium hydroxide.

The reaction partners are reacted between 0 ° and 150 ° C., but generally between room temperature and the reflux temperature of the corresponding reaction mixture. The compounds of the general formulas II and III can be prepared using known methods.

For the synthesis of the compounds according to the invention, the reactants are used in approximately equivalent amounts. Suitable reaction media are solvents which are inert towards the reactants. The choice of solvent or suspension medium depends on the use of the corresponding benzyl halides, the acid acceptors used and the metal compounds.

Examples of solvents or suspending agents that may be mentioned are ethers, such as diethyl ether, diisopropyl ether, tetrahydrofuran and dioxane, aliphatic and aromatic hydrocarbons, such as petroleum ether, cyclohexane, hexane, heptane, benzene, toluene and xylene, carboxylic acid nitriles, such as acetonitrile, and carboxamides.

However, as such, the reactants can themselves have a solvent function.

Tertiary amines, for example triethylamine or N, N-dimethylaniline and pyridine bases, or preferably inorganic bases suitable for this purpose, such as oxides, hydroxides, hydrides, carbonates and alcoholates of the alkali and alkaline earth metals, are used to bind the corresponding hydrohalic acids.

The etherification of the xylitol compounds of the general formula II with benzyl halides of the general formula III, where Y again represents a hydroxyl group and X a halogen atom, can also be carried out with phase transfer catalysis in a manner known per se. This process allows the compounds according to the invention to be prepared more simply and in higher yield using cheaper materials.

According to the invention, a benzyl halide of the formula is used for this purpose III

in a two-phase system, consisting of a xylitol compound of the formula III, optionally diluted by an inert solution medium, and an alkali hydroxide, solid or as an aqueous solution, reacted in the presence of a catalyst. Of the hydroxides, sodium hydroxide, preferably as a 50% strength aqueous solution, is preferred.

Onium compounds such as quaternary ammonium, phosphonium and arsonium compounds and sulfonium compounds are suitable as catalysts.

Also suitable are polyglycol ethers, especially cyclic ones such as 18-crown-6, and tertiary amines such as tributylamine. Preferred compounds are quaternary ammonium compounds such as benzyltriethylammonium chloride and tetrabutylammonium bromide.

The proportions of the reactants can be varied within wide limits. The reactions are preferably carried out with a 1-10-fold excess of benzyl halide and a 1-10-fold excess of hydroxide. 0.02 equivalents of the catalyst are sufficient.

The reaction takes place between 20 and 100 ° C, in general but between 20 and 60 ° C. The reaction time is 1 to 72 hours. Thorough mixing is necessary during the entire reaction time.

The process variants shown above also apply in the event that compounds of the general formula II, where Y is a halogen atom, are reacted with compounds of the general formula III, where X is a hydroxyl group.

For the synthesis of the compounds according to the invention according to process alternative B, the reactants are used in approximately equimolar amounts, although the carbonyl components V and VI or the acetal or ketal components VII and VIII can be used in excess, quasi as a solvent, without disadvantage.

The reaction takes place in the presence of dehydrating agents and acidic catalysts such as copper sulfate, zinc chloride, ammonium chloride, sulfuric acid, p-toluenesulfonic acid, boron trifluoride-diethyl ether complex, hydrogen chloride and phosphorus pentoxide. Suitable reaction media are solvents which are inert towards the reactants. As such are for example, halogenated hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride, aliphatic and aromatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, benzene, toluene and xylene, and the reacting ketones and aldehydes and ketals and acetals themselves.

The reaction takes place between 0 ° and 100 ° C., but generally between room temperature and the reflux temperature of the corresponding reaction mixture. The reaction time is 1 to 72 hours.

The compounds according to the invention prepared by the abovementioned processes can be isolated from the reaction mixture by the customary processes, for example by distilling off the solvent used under normal or reduced pressure, by precipitation with water or by extraction. An increased degree of purity can generally be obtained by column chromatographic purification and by fractional distillation under reduced pressure.

The compounds according to the invention are generally almost colorless and odorless liquids that are sparingly soluble in water, partially soluble in aliphatic hydrocarbons such as petroleum ether, hexane, pentane and cyclohexane, readily soluble in halogenated hydrocarbons such as chloroform, methylene chloride and carbon tetrachloride, aromatic hydrocarbons such as benzene, toluene and xylene, ethers such as diethyl ether, tetrahydrofuran and dioxane, carboxylic acid nitriles such as acetonitrile, ketones such as acetone, alcohols such as methanol and ethanol, carboxamides such as dimethylformamide, and sulfoxides such as dimethyl sulfoxide.

As already mentioned, the compounds according to the invention occur as optical, optionally also as geometric isomers. The individual isomers and their mixtures are also part of the subject matter of the invention.

The following examples illustrate the preparation of the compounds according to the invention.

example 1

5-0- (2,4-dichlorobenzyl) -1,2: 3,4-bis-O-isopropylidene-xylitol

116.13 g (0.5 mol) of 1,2: 3,4-bis-O-isopropylidene-xylitol are added together with 97.74 g (0.5 mol) of 2,4-dichlorobenzyl chloride and 4.5 g (0.019 Mol) submitted benzyltriethylammonium chloride. A solution of 100 g of sodium hydroxide (2.5 mol) in 125 ml of water is added dropwise to this at room temperature with extremely vigorous stirring, the temperature slowly rising to about 50 ° C. and falling back to room temperature over the course of about an hour. Then, to complete the reaction, stirring is continued for a further hour at room temperature, then diluted with 500 ml of ice water and the reaction mixture is extracted three times with 150 ml of ethyl acetate each time. The organic phase is washed twice with 300 ml of water each time, dried over magnesium sulfate, filtered and evaporated at 40 ° C. in vacuo. The remaining oil is fractionally distilled.

Yield: 168.2 g = 86.1% of theory

Bp [low] 0.05 torr: 159-161 ° C; n [low] D [high] 20: 1.5078

TLC: mobile phase = toluene / ethyl acetate 4: 1

R [low] f-value: 0.52

Analysis: Calculated: C 55.25% H 6.18% Cl 18.12%

Found: C 55.62% H 6.42% Cl 17.88%

Example 2

5-0- (2,6-dichlorobenzyl) -1,2: 3,4-bis-O-isopropylidene-xylitol

A solution of 23.2 g (0.1 mol) 1,2: 3,4-bis-O-isopropylidene-xylitol in 100 ml toluene is slowly stirred into a suspension of 2.88 (0.12 mol) sodium hydride added dropwise in 50 ml of toluene. When the addition is complete, the mixture is refluxed for two hours. A solution of 19.54 g (0.1 mol) of 2,6-dichlorobenzyl chloride in 50 ml of toluene is then added dropwise and the mixture is refluxed for a further five hours. After cooling, the mixture is washed three times with 150 ml of water each time; the organic phase is then dried over magnesium sulfate, filtered and concentrated in vacuo at 40.degree. The remaining oil is distilled in vacuo.

Yield: 35.8 g = 91.5% of theory

Bp [low] 1 Torr: 190-98 ° C; n [low] D [high] 20: 1.5080

TLC: mobile phase = toluene / ethyl acetate 4: 1

R [low] f-value: 0.50

Analysis: Calculated: C 55.25% H 6.18% Cl 18.12%

Found: C 55.66% H 6.46% Cl 18.03%

Example 3

5-0- (2-chlorobenzyl) -1,2: 3,4-bis-O-isopropylidene-xylitol

A solution of 11.64 g (0.05 mol) 1,2: 3,4-bis-O-isopropylidene-xylitol in 30 ml dry dimethylformamide is carefully mixed with 1.44 g (0.06 mol) sodium hydride. The mixture is then subsequently stirred at 40.degree. C. for one hour. 8.1 g (0.05 mol) of 2-chlorobenzyl chloride are then added dropwise, the temperature rising to 55.degree. To complete the reaction, the mixture is subsequently stirred at 50 ° C. for a further 2.5 hours; then carefully diluted with 150 ml of ice water and extracted three times with 200 ml of ethyl acetate each time. The ethyl acetate phase, dried over magnesium sulfate and filtered, is evaporated at 40 ° C. in vacuo. The oily residue is distilled in a bulb tube (oven temperature: 160 ° C.; 0.1-0.05 Torr).

Yield: 15.4 g = 86.3% of theory

n [low] D [high] 20: 1.4978

TLC: mobile phase = toluene / ethyl acetate 4: 1

R [low] f-value: 0.50

Analysis: Calculated: C 60.57% H 7.06% Cl 9.94%

Found: C 60.50% H 6.98% Cl 9.70%

Example 4

5-0- (2,4-dichlorobenzyl) -1,2: 3,4-bis-O- (methyl-methylene) -xylitol

9.32 g (0.03 mol) of 5-O- (2,4-dichlorobenzyl) xylitol are suspended in a solution of 9.44 g (0.08 mol) of acetaldehyde diethyl acetal and 30 ml of toluene and then with 1 ml of boron trifluoride -Diethyl ether complex added. The mixture is then heated to 80 ° C. for 30 minutes and the alcohol formed is distilled off. After cooling, the reaction solution is washed with saturated potassium hydrogen carbonate solution, dried over magnesium sulfate, filtered and evaporated at 40 ° C. in vacuo. The remaining oil is distilled on a bulb tube (oven temperature: 190 ° C.; 0.01 torr).

Yield: 8.89 g = 81.5% of theory

n [low] D [high] 20: 1.5283

TLC: mobile phase = chloroform / methanol 4: 1

R [low] f value: 0.71

Analysis: Calculated: C 52.90% H 5.55% Cl 19.52%

Found: C 52.97% H 5.75% Cl 19.54%

The following compounds according to the invention can be prepared in an analogous manner.

Name Physical constant

_______________________________________________________________________________________________

5-0- (4-bromobenzyl) -1,2: 3,4-bis-O -isopropylidene-xylitol n [low] D [high] 20: 1.5074

5-0- (3,4-Dichlorobenzyl) -1,2: 3,4-bis-O -isopropylidene-xylitol n [low] D [high] 20: 1.5078

5-0- (4-Chlorobenzyl) -1,2: 3,4-bis-O -isopropylidene-xylitol n [low] D [high] 20: 1.4975

5-0- (2-Chlorobenzyl) -1,2: 3,4-bis-O-isopropylidene-xylitol n [low] D [high] 20: 1.4978

5-0- (3-chlorobenzyl) -1,2: 3,4-bis-O-isopropylidene-xylitol n [low] D [high] 20: 1.5050

5-0- (2-Methylbenzyl) -1,2: 3,4-bis-O -isopropylidene-xylitol n [low] D [high] 20: 1.4904

5-0- (3-Methylbenzyl) -1,2: 3,4-bis-O -isopropylidene-xylitol n [low] D [high] 20: 1.4878

5-0- (4-Methylbenzyl) -1,2: 3,4-bis-O -isopropylidene-xylitol n [low] D [high] 20: 1.4875

5-0- (3,4-Dimethylbenzyl) -1,2: 3,4-bis-O -isopropylidene-xylitol n [low] D [high] 20: 1.4920

5-0- (2-fluorobenzyl) -1,2: 3,4-bis-O-isopropylidene-xylitol n [low] D [high] 20: 1.4805

5-0- (3-fluorobenzyl) -1,2: 3,4-bis-O-isopropylidene-xylitol n [low] D [high] 20: 1.4798

Name Physical constant

______________________________________________________________________________________________

5-0- (4-Fluorobenzyl) -1,2: 3,4-bis-O-isopropylidene-xylitol n [low] D [high] 20: 1.4789

5-O- (3-trifluoromethylbenzyl) -

1.2: 3,4-bis-O-isopropylidene-xylitol n [low] D [high] 20: 1.4610

5-0-Benzyl-1,2: 3,4-bis-O-isopropylidene-xylitol n [low] D [high] 20: 1.4890

5-0- (2,4-dichlorobenzyl) -1.2: 3.4-

-bis-O- (diethyl-methylene) -xylitol n [low] D [high] 20: 1.5070

5-0- (2,6-dichlorobenzyl) -1.2: 3.4-

-bis-O- (ethyl-methyl-methylene) -xylitol n [low] D [high] 20: 1.5078

5-0- (2,4-dichlorobenzyl) -1.2: 3.4-

-bis-O- (ethyl-methyl-methylene) -xylitol n [low] D [high] 20: 1.5060

5-O- (2-chlorobenzyl) -1,2: 3,4-bis-

-O- (ethyl-methyl-methylene) -xylitol n [low] D [high] 20: 1.4960

4-O- (2-methylbenzyl) -1,2: 3,4-bis-

-O- (ethyl-methyl-methylene) -xylitol n [low] D [high] 20: 1.4847

5-0- (2,6-dichlorobenzyl) -1.2: 3.4-

-bis-O- (methyl-propyl-methylene) -xylitol n [low] D [high] 20: 1.5036

Name Physical constant

_______________________________________________________________________________________________

5-0- (2,4-dichlorobenzyl) -1.2: 3.4-

-bis-O- (methyl-propyl-methylene) -xylitol n [low] D [high] 20: 1.5032

5-O- (2-methylbenzyl) -1,2: 3,4-bis-

-O- (methyl-propyl-methylene) -xylitol n [low] D [high] 20: 1.4884

5-O- (2-chlorobenzyl) -1,2: 3,4-bis-

-O- (methyl-propyl-methylene) -xylitol n [low] D [high] 20: 1.4911

5-0- (2,6-dichlorobenzyl) -1.2: 3.4-

-bis-O- (diethyl-methylene) -xylitol n [low] D [high] 20: 1.5070

5-O- (2-methylbenzyl) -1,2: 3,4-bis-

-O- (diethyl-methylene) -xylitol n [low] D [high] 20: 1.4902

5-O- (2-chlorobenzyl) -1,2: 3,4-bis-

-O- (diethyl-methylene) -xylitol n [low] D [high] 20: 1.4980

The starting compounds for the preparation of the compounds according to the invention are known per se or can be prepared by processes known per se as described in J. Chem. Soc. (London) 1965, 3382.

The following examples explain the preparation of the starting compounds.

A. Compounds of the general formula II

a) 1,2: 3,4-Bis-O- (ethyl-methyl-methylene) -xylitol

50 g (0.328 mol) of xylitol are suspended in 1 l of dry ethyl methyl ketone at room temperature. While stirring well, 10 ml of conc. Sulfuric acid added.

The mixture is stirred for 48 hours at room temperature, after about 5 hours all of the xylitol has dissolved and the reaction solution is red-brown in color.

After the reaction has ended, the solution is adjusted to pH 8 with about 50 ml of 32% strength sodium hydroxide solution while stirring, the color of the solution again becoming discolored. The aqueous phase is separated off, the organic phase is dried over magnesium sulfate and evaporated at 40 ° C. in a water jet vacuum. The residue is fractionally distilled.

Yield: 63.5 g = 74.4% of theory

Bp [low] 0.6 torr = 118 ° C; n [low] D [high] 20 = 1.457

TLC: mobile phase = toluene / ethyl acetate 4: 1; R [low] f-value = 0.22

Analysis: Calculated: C 59.97% H 9.29% O 30.73%

Found: C 59.50% H 9.41% O 31.12% b) 1,2: 3,4-bis-O- (phenyl-methylene) -xylitol

30 g (0.197 mol) of xylitol are suspended in 150 ml of toluene, and 71.04 g (0.393 mol) of benzaldehyde diethyl acetal are added. 150 mg of p-toluenesulfonic acid hydrate are then added and the reaction mixture is heated to 80 ° C., the xylitol slowly dissolving and the reaction product crystallizing out. It is allowed to cool, the crystals are filtered off with suction, washed with 100 ml of ether and dried to constant weight at 40 ° in vacuo.

Yield: 61.2 g = 94.6% of theory

Mp .: 139 ° C (colorless crystals)

TLC: mobile phase = chloroform / methanol 4: 1

R [low] f-value = 0.59

Analysis: Calculated: C 69.49% H 6.14%

Found: C 69.07% H 6.43%

The following starting products can be represented in an analogous manner.

Name Physical constant

_____________________________________________________________________________________________

1,2: 3,4-bis-O-isopropylidene-xylitol n [low] D [high] 20: 1.4530

Kp [deep] 0.4mm: 103 - 105 ° C

M.p .: 33 ° C

1,2: 3,4-Bis-O- (diethyl-methylene) -xylitol n [low] D [high] 20: 1.466

Bp [low] 0.4 Torr: 120 ° C

1,2: 3,4-Bis-O- (benzyl-methyl-methylene) -xylitol n [low] D [high] 20: 1.542

Bp [low] 0.01 Torr: 215-20 ° C

1,2: 3,4-Bis-O- (methyl-propyl-methylene) -xylitol n [low] D [high] 20: 1.547

Bp [low] 0.3 Torr: 136 ° C

1,2: 3,4-bis-O- (methyl- (2-phenyl-

ethyl) methylene xylitol n [low] D [high] 20: 1.535

1,2: 3,4-bis-O- (butyl-methyl-

methylene) xylitol n [low] D [high] 20: 1.459

1,2: 3,4-bis-O- (1,1-tetramethylene

methylene) xylitol n [low] D [high] 20: 1.494

Bp [low] 0.1 Torr: 160 ° C

B. Compounds of the general formula IV

5-0- (2,4-dichlorobenzyl) xylitol

10.2 g (0.026 mol) of 5-O- (2,4-dichlorobenzyl) -1.2: 3,4-bis-O-isopropylidene-xylitol are added to 27.7 ml of 1.5N sulfuric acid given at room temperature. The mixture is then heated to 70 ° C. for 2.5 hours with thorough stirring, then the reaction solution is cooled and adjusted to pH 8 with approx. 4 ml of 32% sodium hydroxide solution. It is now extracted twice with 100 ml of ethyl acetate each time. The organic phase is dried over magnesium sulfate, filtered and concentrated in vacuo. Colorless crystals are obtained which are digested with 50 ml of cold diisopropyl ether. Recrystallization from toluene.

Yield: 6.4 g = 79.0% of theory

M.p .: 96-98 ° C

TLC: mobile phase = chloroform / methanol 4: 1

R [low] f-value = 0.330

Analysis: Calculated: C 46.32% H 5.18% Cl 22.79%

Found: C 46.32% H 5.27% Cl 22.45%

The following starting products can be represented in an analogous manner.

Name Physical constant

____________________________________________________________________________________________

5-0- (2,6-dichlorobenzyl) -xylitol m.p .: 82-83 ° C

5-O- (2-chlorobenzyl) -xylitol m.p .: 52-54 ° C

5-0- (2-Methylbenzyl) -xylitol m.p .: 59-61 ° C

The following examples explain the possible uses of the compounds according to the invention.

Example 5

Growth modifications in cress

In the laboratory, cress seeds are treated with an aqueous emulsion of the agents according to the invention.

The concentration of the active ingredients in the emulsion was 100 ppm.

For this purpose, a slide was placed in a 200 ml glass nozzle with 10 ml active substance emulsion. Filter paper was attached to the slide. When the filter paper was soaked with the solution, 10 cress seeds were evenly distributed on it. Then the lid of a Petri dish was placed on the nozzle. Two glass nozzles were used for each substance.

For evaluation, the lengths of the shoots and roots of the germinated seeds were measured after 7 days.

The average values in cm obtained in this way can be found in the table. This table shows the values in

Relation to the control set and given in percentages.

It turns out that the compounds according to the invention exert a strong influence on the growth of roots and shoots in cress. This becomes clear in the promotion (> 100%) or inhibition (<100%) of the individual parts.

Compound According to the Invention Growth in%

Sprout root

__________________________________________________________________________________________

5-O- (4-bromobenzyl) -1,2: 3,4-bis-

-O-isopropylidene-xylitol 75 138

5-0- (2,6-dichlorobenzyl) -1.2: 3.4-

-bis-O-isopropylidene-xylitol 75 125

5-0- (3,4-dichlorobenzyl) -1.2: 3.4-

-bis-O-isopropylidene-xylitol 88 100

5-0- (2,4-dichlorobenzyl) -1.2: 3.4-

-bis-O-isopropylidene-xylitol 75 88

5-O- (4-chlorobenzyl) -1,2: 3,4-bis-

-O-isopropylidene-xylitol 75 275

5-O- (2-chlorobenzyl) -1,2: 3,4-bis-

-O-isopropylidene-xylitol 88 113

5-O- (3-chlorobenzyl) -1,2: 3,4-bis-

-O-isopropylidene-xylitol 88 200

5-O- (2-methylbenzyl) -1,2: 3,4-bis-

-O-isopropylidene-xylitol 100 225

Compound According to the Invention Growth in%

Sprout root

____________________________________________________________________________________________

5-O- (3-methylbenzyl) -1,2: 3,4-bis-

-O-isopropylidene-xylitol 88 138

5-O- (4-methylbenzyl) -1,2: 3,4-bis-

-O-isopropylidene-xylitol 88 125

5-0- (3,4-dimethylbenzyl) -1,2: 3,4-

-bis-O-isopropylidene-xylitol 88 200

5-O- (2-fluorobenzyl) -1,2: 3,4-bis-

-O-isopropylidene-xylitol 88 250

5-O- (3-fluorobenzyl) -1,2: 3,4-bis-

-O-isopropylidene-xylitol 88 150

5-O- (4-fluorobenzyl) -1,2: 3,4-bis-

-O-isopropylidene-xylitol 100 113

5-O- (3-trifluoromethylbenzyl) -

1,2: 3,4-di-O-isopropylidene xylitol 71 114

5-O-Benzyl-1,2: 3,4-bis-O- (isopropyl-

iden) -xylitol 83 156

5-O- (2,4-dichlorobenzyl) -1,2: 3,4-bis-

- (diethyl methylene) xylitol 83 122

5-O- (2-methylbenzyl) -1,2: 3,4-bis-O-

(ethyl-methyl-methylene) -xylitol 100 89

5-0- (2,4-dichlorobenzyl) -1.2: 3.4-

bis-O- (methyl-propyl-methylene) -xylitol 100 89

5-O- (2-methylbenzyl) -1,2: 3,4-bis-O-

(methyl-propyl-methylene) -xylitol 80 17

Compound According to the Invention Growth in%

Sprout root

_____________________________________________________________________________________________

5-O- (2,6-dichlorobenzyl) -1,2: 3,4-bis-O-

- (diethylenemethylene) xylitol 100 171

5-O- (2-methylbenzyl) -1,2: 3,4-bis-O-

(diethyl methylene) xylitol 83 186

5-O- (2-chlorobenzyl) -1,2: 3,4-bis-O- (di-

ethyl methylene xylitol 100 114

5-O- (2,4-dichlorobenzyl) -1,2: 3,4-bis-

O- (methyl-methylene) -xylitol 83 143

Example 6

Increased chlorophyll levels in soy leaves

Soybean plants about 1 week old were treated in the greenhouse with an aqueous emulsion of the compounds according to the invention. The concentration was the equivalent of about 0.8 kg of AS / 500 l of spray liquor.

After 7 weeks of culture, leaf disks with a diameter of 1.7 cm were punched out of the fifth developed leaf (i.e. the 3rd leaflet). Then the chlorophyll of the disks was ethanol extracted. The amount of chlorophyll in the extract was photo- determined metrically.

The table shows the percentages of chlorophyll a in comparison to the control for the individual treatments. An increased content is indicated by values above 100%.

Compounds According to the Invention Chlorophyll content in

% of control

__________________________________________________________________________________________

5-0- (2,6-dichlorobenzyl) -1,2: 3,4-di-

O-isopropylidene xylitol 290

5-O- (2,6-dichlorobenzyl) -1,2: 3,4-bis-O-

- (ethyl-methyl-methylene) -xylitol 262

5-O- (2,4-dichlorobenzyl) -1,2: 3,4-bis-O-

- (ethyl-methyl-methylene) -xylitol 154

5-O- (2-chlorobenzyl) -1,2: 3,4-bis-O- (ethyl-

-methyl-methylene) -xylitol 126

5-O- (2,6-dichlorobenzyl) -1,2: 3,4-bis-O-

- (methyl-propyl-methylene) -xylitol 174

control

Example 7

Influence the growth of cucumber, French beans and soy

With an application rate of 1 kg of emulsified active ingredient per 500 l of spray liquor, cucumbers, French beans and soybeans were sprayed in two different stages of development. Spraying took place 3 and 8 days after sowing. 3 weeks later, the average length of the plant, the number of internodes and the number of flower buds per plant were recorded.

The following table shows the results.

The percentages given therein result from the relation of the results to the control.

These figures show that the compounds mentioned lead to growth inhibition (length <100) with an often almost constant number of internodes. In the experiment, the number of flower buds was also increased in the case of French beans (> 100).

Example 8

Growth regulation in soy branching

Soy seeds were dressed with the powdery formulated compounds according to the invention at an application rate of 25 and 250 mg of active substance per 100 kg of seed. Each 7 dressed seeds were placed in culture dishes with 500 ml of soil. After 5 weeks of culture in the greenhouse, the growth and morphological peculiarities of the plants were rated.

The following table shows the results. The average values per plant are given.

It is obvious that branching of the plants is strongly promoted in the application indicated. This comes among other things. expressed in the lengths of the branches from the cotyledon axils. This can also affect the number of internodes per plant.

Example 9

Growth regulatory effects in soy - Accelerated development of the generative phase.

Soybeans were grown in culture dishes under greenhouse conditions. Two weeks after sowing, the emulsified active ingredients were sprayed onto the plants in various amounts. 7 weeks after sowing, the length of the plants, the number of flowers and flower buds and the number of pods and pod attachments were recorded.

The table below shows the results of this experiment in the form of percentages relating to the control.

They show that, in addition to the previously described growth inhibition (length <100) and promotion of branching (> 100), the generative phase is influenced by the first two compounds. This is evidenced by the increased numbers of pods and pods.

The plants bloom earlier and at the time of the evaluation are in a further development stage than in the control. The comparison substance is phytotoxic and shows a significantly lower growth-regulating effect.

Example 10

Growth regulatory effects in soy

Soybeans were grown under greenhouse conditions. The spray treatment was carried out pre- and post-emergence with various emulsified active ingredients. The number of branches per plant was recorded 6 weeks after sowing.

The following table shows the results.

The compounds according to the invention are superior to the comparison agent in terms of their growth-regulating effect.

Dose according to the invention branches each

Compounds (kg active ingredient / ha) plant

Pre-emergence post-emergence

______________________________________________________________________________________________________

5-O- (2,6-dichlorobenzyl) -

-1.2: 3,4-bis-O-isopropyl-1 4 0.5

-iden-xylitol

Comparison means

2.3: 4,6-di-O-isopropylidene-2.5 0 0.2

-2-ketogulonic acid / sodium salt 5 0 0.2

Control - 0 0

Claims (37)

1. Xylitol derivatives of the general formula I. where R [deep] 1, R [deep] 2, R [deep] 3 and R [deep] 4 are identical or different and each is hydrogen, a C [deep] 1-C [deep] 10-alkyl radical, a or C [deep] 1-C [deep] 10-alkyl radical substituted several times by halogen, C [deep] 1-C [deep] 6-alkoxy, phenoxy and / or halophenoxy, an aryl-C [deep] 1-C [ deep] 3-alkyl radical, an aryl substituted one or more times by C [deep] 1-C [deep] 6-alkyl, halogen, C [deep] 1-C [deep] 6-alkoxy, nitro and / or trifluoromethyl C [deep] 1-C [deep] 3-alkyl radical, a C [deep] 3-C [deep] 8-cycloaliphatic hydrocarbon radical, an aromatic hydrocarbon radical or a single or multiple through C [deep] 1-C [deep] 6-Al- kyl, halogen, C [deep] 1-C [deep] 6-alkoxy, nitro and / or trifluoromethyl substituted aromatic hydrocarbon radical or R [deep] 1 and R [deep] 2 and / or R [deep] 3 and R [deep ] 4 together with the adjacent carbon atom a C [deep] 3-C [deep] 8-cycloaliphatic hydrocarbon radical, R [deep] 5 hydrogen or a C [deep] 1-C [deep] 4-alkyl radical and R [deep ] 6 is an aromatic hydrocarbon radical or one or more times through C [deep] 1-C [deep] 6-alkyl, C [deep] 1-C [deep] 6-alkoxy, phenoxy, phenyl, halogen, nitro and / or Represent trifluoromethyl substituted aromatic hydrocarbon radical. 2. Benzyl ether derivatives of xylitol according to claim 1, wherein R [deep] 1, R [deep] 2, R [deep] 3 and R [deep] 4 are identical or different and are each methyl, ethyl, propyl, isopropyl, n-butyl , sec-butyl, tert-butyl, 2,2-dimethyl-1-propyl, n-pentyl, n-heptyl, n-octyl, n-decyl, chloromethyl, bromomethyl, fluoromethyl, dichloromethyl, trifluoromethyl, trichloromethyl, methoxymethyl , Ethoxymethyl, phenoxymethyl, 4-chlorophenoxymethyl, chloroethyl, bromoethyl, 2-ethoxyethyl, 2-phenoxyethyl, cyclopropyl, cyclopentyl, cyclohexyl, benzyl, 2-phenylethyl, phenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 3 , 4-dichlorophenyl, 4-methoxyphenyl, 4-nitrophenyl, 2,4-dichlorophenyl, R [deep] 5 hydrogen or methyl and R [deep] 6 phenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2,6 -Dichlorophenyl, 2,4-dichlorophenyl, 3,4-di- chlorophenyl, 2,4,6-trichlorophenyl, 4-bromophenyl, 2,4-dibromophenyl, 2,6-dibromophenyl, 2,4,6-tribromophenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2,4- Difluorophenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 3,4-dimethylphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 3,4-dioxymethylene phenyl, 2-phenoxyphenyl, 3-phenoxyphenyl, 2-nitrophenyl, Represent 3-nitrophenyl or 4-nitrophenyl. 3. 5-O- (2,4-dichlorobenzyl) -1,2: 3,4-bis-O-isopropylidene-xylitol 4. 5-O- (2,6-dichlorobenzyl) -1,2: 3,4-bis-O-isopropylidene-xylitol 5. 5-O- (2-chlorobenzyl) -1,2: 3,4-bis-O-isopropylidene-xylitol 6. 5-O- (2,4-dichlorobenzyl) -1,2: 3,4-bis-O- (methyl-methylene) -xylitol 7. 5-O- (4-bromobenzyl) -1,2: 3,4-bis-O-isopropylidene-xylitol 8. 5-O- (3,4-dichlorobenzyl) -1,2: 3,4-bis-O-isopropylidene-xylitol 9. 5-O- (4-chlorobenzyl) -1,2: 3,4-bis-O-isopropylidene-xylitol 10. 5-O- (2-chlorobenzyl) -1,2: 3,4-bis-O-isopropylidene-xylitol 11. 5-O- (3-chlorobenzyl) -1,2: 3,4-bis-O-isopropylidene-xylitol 12. 5-O- (2-methylbenzyl) -1,2: 3,4-bis-O-isopropylidene-xylitol 13. 5-0- (3-Methylbenzyl) -1,2: 3,4-bis-O-isopropylidene-xylitol 14. 5-0- (4-Methylbenzyl) -1,2: 3,4-bis-O-isopropylidene-xylitol 15. 5-0- (3,4-Dimethylbenzyl) -1,2: 3,4-bis-O-isopropylidene-xylitol 16. 5-O- (2-fluorobenzyl) -1,2: 3,4-bis-O-isopropylidene-xylitol 17. 5-O- (3-fluorobenzyl) -1,2: 3,4-bis-O-isopropylidene-xylitol 18. 5-O- (4-fluorobenzyl) -1,2: 3,4-bis-O-isopropylidene-xylitol 19. 5-O- (3-trifluoromethylbenzyl) -1,2: 3,4-bis-O-isopropylidene-xylitol 20. 5-O-Benzyl-1,2: 3,4-bis-O-isopropylidene-xylitol 21. 5-O- (2,4-dichlorobenzyl) -1,2: 3,4-bis-O- (diethyl-methylene) -xylitol 22. 5-O- (2,6-dichlorobenzyl) -1,2: 3,4-bis-O- (ethyl-methyl-methylene) -xylitol 23. 5-O- (2,4-dichlorobenzyl) -1,2: 3,4-bis-O- (ethyl-methyl-methylene) -xylitol 24. 5-O- (2-chlorobenzyl) -1,2: 3,4-bis-O- (ethyl-methyl-methylene) -xylitol 25. 5-O- (2-methylbenzyl) -1,2: 3,4-bis-O- (ethyl-methyl-methylene) -xylitol 26. 5-O- (2,6-dichlorobenzyl) -1,2: 3,4-bis-O- (methyl-propyl-methylene) -xylitol 27. 5-0- (2,4-Dichlorobenzyl) -1,2: 3,4-bis-O- (methyl-propyl-methylene) -xylitol 28. 5-O- (2-methylbenzyl) -1,2: 3,4-bis-O- (methyl-propyl-methylene) -xylitol 29. 5-O- (2-chlorobenzyl) -1,2: 3,4-bis-O- (methyl-propyl-methylene) -xylitol 30. 5-O- (2,6-dichlorobenzyl) -1,2: 3,4-bis-O- (diethyl-methylene) -xylitol 31. 5-O- (2-methylbenzyl) -1,2: 3,4-bis-O- (diethyl-methylene) -xylitol 32. 5-O- (2-chlorobenzyl) -1,2: 3,4-bis-O- (diethyl-methylene) -xylitol 33. Process for the preparation of xylitol derivatives according to Claims 1 to 32, characterized in that one A) Compounds of the general formula II with compounds of the general formula III in the presence of acid binders or B) compounds of the general formula IV a) with compounds of the general formulas V and VI in the presence of acidic catalysts and dehydrating agents or b) with compounds of the general formulas VII and VIII in the presence of acidic catalysts, where R [deep] 1, R [deep] 2, R [deep] 3, R [deep] 4, R [deep] 5 and R [deep] 6 have the meaning given above, R [deep] 7 and R [deep] 8 are identical or different and represent C [deep] 1-C [deep] 4-alkyl and X and Y are different and each represent a halogen atom or the group OZ in which Z is a hydrogen atom or represent an equivalent of an alkali or alkaline earth metal, preferably a sodium, potassium or lithium atom. 34. Agent with a growth-regulating effect for plants, characterized by a content of at least one compound according to Claims 1 to 32. 35. Agent with a growth-regulating effect for plants according to claim 34 in a mixture with carriers and / or auxiliaries. 36. Agent according to claims 34 and 35 for influencing vegetative and generative growth in legumes, in particular soy. 37. Agent having a growth-regulating effect for plants according to claim 34, produced by the method according to claim 33.